WO2013125659A1 - Pâte de poudre de métal et son procédé de production - Google Patents

Pâte de poudre de métal et son procédé de production Download PDF

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Publication number
WO2013125659A1
WO2013125659A1 PCT/JP2013/054415 JP2013054415W WO2013125659A1 WO 2013125659 A1 WO2013125659 A1 WO 2013125659A1 JP 2013054415 W JP2013054415 W JP 2013054415W WO 2013125659 A1 WO2013125659 A1 WO 2013125659A1
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Prior art keywords
metal powder
acid
copper powder
paste
treated
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PCT/JP2013/054415
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English (en)
Japanese (ja)
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秀樹 古澤
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Jx日鉱日石金属株式会社
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Priority to KR1020147024611A priority Critical patent/KR101769337B1/ko
Priority to JP2014500934A priority patent/JP6212480B2/ja
Priority to CN201380010167.XA priority patent/CN104115237B/zh
Publication of WO2013125659A1 publication Critical patent/WO2013125659A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/005—Electrodes
    • H01G4/008—Selection of materials
    • H01G4/0085—Fried electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/228—Terminals
    • H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/10—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/15—Nickel or cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru

Definitions

  • the present invention relates to a metal powder paste suitable for manufacturing a chip multilayer ceramic capacitor electrode, and a method for manufacturing the same.
  • Chip monolithic ceramic capacitors are electronic components used in many electronic devices due to their small size and large capacity.
  • Chip monolithic ceramic capacitors have a structure in which ceramic dielectrics and internal electrodes are stacked and integrated in layers, and each laminated layer constitutes a capacitor element, and these elements are electrically connected in parallel by external electrodes. As a whole, it becomes one small and large-capacity capacitor.
  • a dielectric sheet is manufactured as follows. That is, first, an organic binder and a solvent as a dispersing agent and a molding aid are added to a dielectric raw material powder such as BaTiO 3 , and a slurry is obtained through pulverization, mixing, and defoaming steps. Thereafter, the slurry is thinly spread on a carrier film such as a PET film and applied by a coating method such as a die coater. It is dried to obtain a thin dielectric sheet (green sheet).
  • the metal powder that is a raw material of the internal electrode of the chip multilayer ceramic capacitor is mixed with an organic binder and a solvent as a dispersing agent or a molding aid and a defoaming step, as in the case of the dielectric raw material powder,
  • the resulting copper powder paste (copper paste).
  • the internal electrode is printed on a green sheet (dielectric sheet) mainly by screen printing, and after drying, the printed green sheet is peeled off from the carrier film, and a large number of such green sheets are laminated. .
  • the green sheets thus laminated are integrated by applying a pressing pressure of several tens to several hundreds of MPa, and then cut into individual chips. Thereafter, the internal electrode layer and the dielectric layer are sintered at a high temperature of about 1000 ° C. in a firing furnace. In this way, a chip multilayer ceramic capacitor is manufactured.
  • Pt was used for the internal electrode of such a chip multilayer ceramic capacitor.
  • Pd, Pd—Ag alloy, and currently Ni is mainly used from the viewpoint of cost.
  • Ni is replaced with Cu, in principle, low inductance can be realized for high frequency applications.
  • Cu has an advantage that the cost is lower than that of Ni.
  • the melting point of Cu is lower than that of Pt, Pd, and Ni in the first place. Furthermore, when Cu is employed as the internal electrode powder due to a decrease in melting point caused by an increase in surface area due to the reduction in particle diameter as described above, the melting of Cu powder at a lower temperature during firing is performed. Begins. This induces the generation of cracks in the electrode layer itself. Further, since the electrode layer contracts rapidly after the temperature is lowered, there is a possibility that the dielectric layer and the electrode layer are separated (delamination). In order to avoid such inconveniences, the metal powder for internal electrodes is required to have a heat shrinkage characteristic equivalent to that of a dielectric, and an index representing this is a sintering start temperature.
  • Patent Document 1 (Patent No. 4001438) disperses Cu powder in a liquid, adds an aqueous solution of a water-soluble salt of a metal element to this, adjusts the pH to fix the metal oxide to the surface of the Cu powder, This is a technology for strengthening the adhesion of the surface treatment layer by causing these surface treatment copper powders to collide with each other.
  • the process is composed of adsorption of metal oxide to copper powder and adhesion strengthening, there is a problem in terms of productivity.
  • the particle size of the copper powder is further smaller than 0.5 ⁇ m, the size of the metal oxide particles to be adsorbed becomes close, so that it is expected that the adsorption of the oxide itself to the copper powder becomes difficult.
  • Patent Document 2 Japanese Patent No. 4164209 is a technique for coating copper powder with silicone oil having a specific functional group.
  • oil and Cu powder are mixed, it is easy to aggregate and there is a problem in terms of workability.
  • separation of oil and Cu powder is difficult, and there exists a problem in the point of workability
  • Patent Document 3 is a technique for forming an SiO 2 gel coating film by subjecting alkoxysilane hydrolyzed on the surface of copper powder to condensation polymerization using an ammonia catalyst.
  • NH 3 as a catalyst when applied to copper powder having a particle size of 1 ⁇ m or less, NH 3 as a catalyst must be continuously added so as to prevent agglomeration, but reaction control depends on the skill of the specific operation skill of addition. It is very difficult, and there are problems in terms of workability and productivity.
  • an object of the present invention is to provide a surface-treated copper powder paste excellent in sintering retardancy, which can be suitably used for the production of a chip multilayer ceramic capacitor electrode, and a method for producing the same. .
  • the present inventors mixed copper powder and aminosilane aqueous solution and adsorbed aminosilane to the copper powder surface, so that there was no aggregation after the surface treatment, thereby dramatically improving the sintering delay. It was found that a copper powder paste was obtained, and the present invention was reached. Furthermore, this copper powder paste is obtained by blending a fatty acid when dispersing the surface-treated copper powder in a solvent, but the aggregation of the surface-treated copper powder is greatly reduced by the blending of this fatty acid. It was a thing. These manufacturing operations are very simple, do not require advanced skills, are excellent in workability, and are excellent in productivity.
  • the copper powder paste obtained by the surface-treated copper powder obtained in this manner exhibits a high sintering start temperature despite being a copper powder paste using copper powder having small particles. It was. Furthermore, even when a metal powder other than copper powder is similarly surface-treated, and when it is surface-treated with a coupling agent other than aminosilane, a surface-treated metal powder having excellent characteristics is obtained. It was found that a metal powder paste with excellent characteristics can be obtained.
  • the present invention includes the following (1) to (36).
  • the surface-treated copper powder is any one of (1) to (10), wherein the amount of aminosilane used for the surface treatment is 0.01 mL or more with respect to 1 g of the copper powder. Copper powder paste. (12) The copper powder paste according to (11), wherein the surface-treated copper powder is a copper powder having an aminosilane amount of 0.05 mL or more, surface-treated with mixing and stirring time of 30 minutes or less with the copper powder. (13) The copper powder paste according to any one of (4) to (11), wherein the aminosilane is monoaminosilane or diaminosilane.
  • the copper powder paste according to any one of (1) to (13), wherein the surface-treated copper powder is a copper powder obtained by surface-treating raw material copper powder obtained by a wet method.
  • the copper powder paste according to any one of (1) to (14), wherein the surface-treated copper powder has a D50 ⁇ 1.5 ⁇ m.
  • the copper powder paste according to any one of (1) to (14), wherein the surface-treated copper powder has a D50 ⁇ 1.0 ⁇ m.
  • the copper powder paste according to any one of (1) to (14), wherein the surface-treated copper powder has D50 ⁇ 0.5 ⁇ m and Dmax ⁇ 1.0 ⁇ m.
  • the copper powder paste according to (22), wherein the fatty acid is a C3-C24 saturated or unsaturated fatty acid.
  • the copper powder paste according to (22), wherein the fatty acid is a C3 to C24 fatty acid having 0 to 2 double bonds.
  • Fatty acids are crotonic acid, acrylic acid, methacrylic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, vaccenic acid, linoleic acid , (9,12,15) -linolenic acid, (6,9,12) -linolenic acid, dihomo- ⁇ -linolenic acid, eleostearic acid, tuberculostearic acid, arachidic acid (eicosanoic acid), 8,11 1 selected from the group consisting of eicosadienoic acid, 5,8,11-eicosatrienoic acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, elaidic acid, erucic acid, docosahexaenoic acid,
  • the solvent is an alcohol solvent, a glycol ether solvent, an acetate solvent, a ketone solvent, or a hydrocarbon solvent.
  • the alcohol solvent is at least one selected from the group consisting of terpineol, dihydroterpineol, isopropyl alcohol, butyl carbitol, terpineloxyethanol, dihydroterpineloxyethanol.
  • the acetate solvent is at least one selected from the group consisting of butyl carbitol acetate, dihydroterpineol acetate, terpineol acetate, dihydrocarbyl acetate, and carbyl acetate.
  • the ketone solvent is methyl ethyl ketone.
  • the copper powder paste according to (27), wherein the hydrocarbon solvent is at least one selected from the group consisting of toluene and cyclohexane.
  • the filter having a pore size of 5 ⁇ m and an effective area of 9.0 cm 2 was filtered under reduced pressure of 0.3 atm, and the percentage of the transmitted mass with respect to 4 g of the input mass (transmittance) was 35% or more after 30 seconds.
  • the present invention also includes the following (41) to (44).
  • (41) A chip multilayer ceramic capacitor manufactured using the paste according to any one of (36).
  • (42) A multilayer substrate on which the chip multilayer ceramic capacitor according to (41) is mounted on an outermost layer.
  • (43) A multilayer substrate on which the chip multilayer ceramic capacitor according to (41) is mounted on an inner layer.
  • (44) (42) or an electronic component on which the multilayer substrate according to (43) is mounted.
  • the present invention also includes the following (51) to (59).
  • (51) A surface-treated copper powder having an adhesion amount of Si of 500 to 16000 ⁇ g with respect to 1 g of copper powder and a weight percentage of N with respect to the copper powder being 0.05% or more;
  • the process of preparing the paste A surface-treated copper powder having an adhesion amount of Si of 500 to 16000 ⁇ g with respect to 1 g of copper powder and a weight percentage of N with respect to the copper powder being 0.05% or more; A step of preparing a paste by dispersing an organic substance having a carboxyl group in a solvent; The method according to (51), wherein (53) The process of preparing the paste The method according to (51), which is a step of preparing a paste by further dispersing a binder resin in a solvent in addition to the surface-treated copper powder and the organic substance having a carboxyl group. (54) The method according to any one of (51) to (53), wherein the organic substance having a carboxyl group is a fatty acid.
  • the present invention also includes the following (61) to (79).
  • (61) Surface treated copper powder A step of mixing copper powder with an aminosilane aqueous solution to prepare a copper powder dispersion; (51) The method according to any one of (51) to (59), which is a surface-treated copper powder produced by a method for producing a surface-treated copper powder.
  • Aminosilane aqueous solution is represented by the following formula I: H 2 N—R 1 —Si (OR 2 ) 2 (R 3 ) (Formula I) (However, in the above formula I, R1 is a linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic, heterocyclic or non-heterocyclic, C1-C12 hydrocarbon. A divalent group, R2 is a C1-C5 alkyl group, R3 is a C1-C5 alkyl group or a C1-C5 alkoxy group.
  • R1 is a substituted or unsubstituted C1-C12 linear saturated hydrocarbon divalent group, a substituted or unsubstituted C1-C12 branched saturated hydrocarbon divalent group, substituted or unsubstituted C1-C12 linear unsaturated hydrocarbon divalent group, substituted or unsubstituted C1-C12 branched unsaturated hydrocarbon divalent group, substituted or unsubstituted C1-C12 ring A group consisting of a divalent group of formula hydrocarbon, a substituted or unsubstituted C1-C12 heterocyclic hydrocarbon divalent group, a substituted or unsubstituted C1-C12 aromatic hydrocarbon divalent group,
  • the method according to (69) which is a group selected from: (71)
  • R1 represents — (CH 2 ) n —, — (CH 2 )
  • the present invention also includes the following (81) to (83).
  • (81) A copper powder paste produced by the production method according to any one of (51) to (57) and (61) to (77).
  • (83) An electrode for a chip multilayer ceramic capacitor produced by the production method according to (79).
  • the present invention also includes the following (91) to (92).
  • (91) A copper powder paste produced by the method according to any one of (51) to (57) and (61) to (77), Copper having a pore size of 5 ⁇ m and an effective area of 9.0 cm 2 under reduced pressure filtration of 0.3 atm, and the percentage (permeability) of the transmitted mass to the input mass of 4 g is 35% or more after 15 minutes. Powder paste.
  • (92) The electrode manufactured by the manufacturing method as described in (78) or (79).
  • the present invention also includes the following (101) to (101).
  • (101) Surface treatment in which the adhesion amount of any one or more of Si, Ti, Al, Zr, Ce, and Sn is 200 to 16000 ⁇ g with respect to 1 g of metal powder, and the weight percentage of N with respect to metal powder is 0.02% or more.
  • Metal powder A metal powder paste containing an organic substance having a carboxyl group dispersed in a solvent.
  • (102) The metal powder paste according to (101), wherein the binder resin is contained in a solvent in addition to the surface-treated metal powder and the organic substance having a carboxyl group.
  • (103) The metal powder paste according to any one of (101) to (102), wherein the metal powder is copper powder.
  • any one of Si, Ti, Al, Zr, Ce, and Sn is at least one of Ti, Al, Zr, Ce, and Sn, and any one of (101) to (109) The metal powder paste as described.
  • the metal powder paste according to any one of (101) to (118), wherein the organic substance having a carboxyl group is a carboxylic acid or an amino acid.
  • Fatty acids are crotonic acid, acrylic acid, methacrylic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, vaccenic acid, linoleic acid , (9,12,15) -linolenic acid, (6,9,12) -linolenic acid, dihomo- ⁇ -linolenic acid, eleostearic acid, tuberculostearic acid, arachidic acid (eicosanoic acid), 8,11 1 selected from the group consisting of eicosadienoic acid, 5,8,11-eicosatrienoic acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, elaidic acid, erucic acid, docosahexaenoic acid,
  • the filter having a pore size of 5 ⁇ m and an effective area of 9.0 cm 2 was filtered under reduced pressure of 0.3 atm, and the percentage of the transmitted mass with respect to 4 g of the input mass (transmittance) was 35% or more after 30 seconds. 101) to (126). (128) (101) A chip multilayer ceramic capacitor manufactured using the paste according to any one of (127). (129) The chip multilayer ceramic capacitor according to (128), wherein any of SiO 2 , TiO 2 , and Al 2 O 3 having a diameter of 10 nm or more is present in the cross section of the internal electrode.
  • Metal powder A step of preparing a paste by dispersing an organic substance having a carboxyl group in a solvent;
  • a method for producing a metal powder paste comprising: (132) The process of preparing the paste The method according to (131), which is a step of preparing a paste by further dispersing a binder resin in a solvent in addition to the surface-treated metal powder and the organic substance having a carboxyl group.
  • (142) The method according to any one of (137) to (141), comprising a step of ultrasonicating the metal powder dispersion.
  • (143) The method according to (142), wherein the ultrasonic treatment is a step of performing ultrasonic treatment for 1 to 180 minutes.
  • (144) A step of collecting the metal powder by filtering the metal powder dispersion, Drying the metal powder collected by filtration to obtain a surface-treated metal powder, The method according to any one of (137) to (143), comprising: (145) The method according to (144), wherein the drying is performed in an oxygen atmosphere or an inert atmosphere.
  • Aminosilane aqueous solution is represented by the following formula I: H 2 N—R 1 —Si (OR 2 ) 2 (R 3 ) (Formula I) (However, in the above formula I, R1 is a linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic, heterocyclic or non-heterocyclic, C1-C12 hydrocarbon.
  • R2 is a C1-C5 alkyl group
  • R3 is a C1-C5 alkyl group or a C1-C5 alkoxy group.
  • R1 represents — (CH 2 ) n —, — (CH 2 ) n — (CH) m — (CH 2 ) j ⁇ 1 —, — (CH 2 ) n — (CC) — (CH 2 ) n ⁇ 1 -, - (CH 2) n -NH- (CH 2) m -, - (CH 2) n -NH- (CH 2) m -NH- (CH 2) j -, - (CH 2) n-1
  • R1 represents — (CH 2 ) n —, — (CH 2 ) n — (CH) m — (CH 2 ) j ⁇ 1 —, — (CH 2 ) n — (CC) — (CH 2 ) n ⁇ 1 -, - (CH 2) n -NH- (CH 2) m -, - (CH 2) n -NH- (CH 2) m -NH- (CH 2) j -, - (CH 2) n-1
  • R1 represents — (CH 2 ) n —, — (CH 2 ) n — (CH) m — (CH 2 ) j ⁇ 1 —, — (CH 2 ) n — (CC) — (CH 2 ) n ⁇ 1 -, - (CH 2) n -NH- (CH 2) m -, - (CH 2) n -NH- (CH 2) m -NH- (CH 2) j -, - (CH
  • Metal powder The method whose sintering start temperature is 400 degreeC or more.
  • the surface-treated copper powder used in the copper powder paste according to the present invention has excellent sintering delay without agglomeration even after the surface treatment, and high sintering start temperature even with a small particle copper powder. Indicates. Therefore, the copper powder paste according to the present invention is excellent in sintering delay and is excellent in the dispersibility of the copper powder in the paste, thus avoiding manufacturing problems such as electrode peeling, Manufacture of the electrode for chip multilayer ceramic capacitors can be performed advantageously.
  • this surface-treated copper powder can be manufactured by performing a very simple treatment on the copper powder as a raw material, and the production of the copper powder paste according to the present invention is performed on this surface-treated copper powder. Since it can be manufactured by performing a very simple process, it does not require a high level of skill and is excellent in workability and productivity. Moreover, according to this invention, metal powder paste which has the characteristic similarly excellent also about metal powders other than copper powder can be obtained.
  • FIG. 1 is a TEM image of a cross section perpendicular to the surface of the surface-treated copper powder.
  • the copper powder is mixed with an aminosilane aqueous solution to prepare a copper powder dispersion, and the surface-treated copper powder can be obtained from this copper powder dispersion.
  • a copper powder paste can be produced by carrying out the step of preparing a paste by dispersing the surface-treated copper powder and the organic substance having a carboxyl group in a solvent.
  • the binder resin in addition to the surface-treated copper powder and the organic substance having a carboxyl group, can be further dispersed in the solvent, and other additives can be added as desired.
  • the surface-treated copper powder can be obtained in detail as described below. Starting from the copper powder used as the raw material for the surface treatment, the raw copper powder is subjected to a surface treatment and then dispersed in a solvent together with an organic substance having a carboxyl group to obtain a copper powder paste. Is within the scope of the present invention. Furthermore, it is also within the scope of the present invention to obtain a copper powder paste starting from the production of raw material copper powder to be subjected to surface treatment.
  • the organic substance having a carboxyl group is preferably an amino acid or a carboxylic acid.
  • the carboxylic acid include fatty acids.
  • amino acids include alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine. it can.
  • fatty acids used in the present invention include saturated or unsaturated fatty acids having C3 to C24 carbon atoms.
  • C3-C24, more preferably C4-C22, more preferably C8-C22, more preferably C12-C22, more preferably C16-C20, particularly preferably C18 fatty acids are used.
  • fatty acids having a double bond number of, for example, 0-4, such as 0-3, such as 0-2, can be used.
  • a fatty acid having one double bond is particularly preferred in that the filter filtration is quick.
  • a lipophilic fatty acid can be used as the fatty acid, and examples of such a fatty acid include fatty acids having the above-mentioned carbon number.
  • such fatty acids include crotonic acid, acrylic acid, methacrylic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearin Acid, oleic acid, vaccenic acid, linoleic acid, (9,12,15) -linolenic acid, (6,9,12) -linolenic acid, dihomo- ⁇ -linolenic acid, eleostearic acid, tuberculostearic acid, Arachidic acid (eicosanoic acid), 8,11-eicosadienoic acid, 5,8,11-eicosatrienoic acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, elaidic acid, erucic acid, docosahexaenoic acid, eicosa
  • the fatty acid is one or more selected from the group consisting of stearic acid, oleic acid, linoleic acid, and acrylic acid, preferably from the group consisting of stearic acid, oleic acid, and linoleic acid.
  • stearic acid oleic acid
  • linoleic acid linoleic acid
  • acrylic acid preferably from the group consisting of stearic acid, oleic acid, and linoleic acid.
  • a fatty acid salt can be used as the fatty acid, in a preferred embodiment, it is preferred that the fatty acid itself is not a fatty acid salt.
  • a solvent used in a screen printing paste of an electronic material can be used.
  • examples of such a solvent include alcohol solvents, glycol ether solvents, acetate solvents, ketone solvents, and Mention may be made of hydrocarbon solvents.
  • examples of the alcohol solvent include terpineol, isopropyl alcohol, and butyl carbitol.
  • examples of terpineol include ⁇ -terpineol, ⁇ -terpineol, and ⁇ -terpineol, and ⁇ -terpineol is particularly preferable.
  • examples of the glycol ether solvent include butyl carbitol.
  • examples of the acetate solvent include butyl carbitol acetate.
  • the ketone solvent examples include methyl ethyl ketone.
  • the hydrocarbon solvent examples include toluene and cyclohexane.
  • the solvent may be one or more selected from the group consisting of terpineol, isopropyl alcohol, butyl carbitol, butyl carbitol acetate, methyl ethyl ketone, toluene, and cyclohexane, and preferably ⁇ -One or more selected from the group consisting of terpineol, butyl carbitol and butyl carbitol acetate can be used.
  • the mass ratio of fatty acid to the surface-treated copper powder is, for example, 1/1000 to 1/10. It can be in the range, preferably in the range of 1/1000 to 1/20.
  • the mass ratio of fatty acid to solvent can be, for example, in the range of 1/100 to 1/10, and preferably in the range of 1/60 to 1/15.
  • the mass ratio of the solvent to the surface-treated copper powder is, for example, in the range of 1/4 to 1/1, preferably 1/3 to 1. /1.5 range.
  • any binder can be used as long as it can improve the adhesion to the substrate.
  • a binder include cellulose resins, epoxy resins, and acrylic resins.
  • a polyvinyl acetal resin, a polyvinyl butyral resin, or an acrylate resin can be used.
  • the operation of preparing a paste by dispersing the surface-treated copper powder, fatty acid and the like in a solvent can be performed by a known dispersing means, and if desired, stirring, kneading, and ultrasonic treatment may be performed.
  • the fatty acid can be added to the solvent simultaneously with the addition of the surface treated copper powder or prior to the addition of the surface treated copper powder.
  • an organic substance having a carboxyl group may be directly adsorbed on the surface-treated copper powder, and then dispersed in a solvent to form a paste.
  • an organic substance having a carboxyl group preferably a fatty acid, is preferably used in the step of dispersing the surface-treated copper powder in a solvent to form a paste. It is preferable to add and adsorb to copper powder.
  • a step of filtering the prepared paste with a filter is performed. . Filtration with such a filter is performed in order to form a fine wiring or an extremely thin conductive layer (electrode) with a copper powder paste.
  • a filter for example, a filter having a pore size of 1 to 8 ⁇ m, preferably 1 to 5 ⁇ m can be used.
  • filtration through a filter is performed by vacuum filtration or pressure filtration.
  • the pressure of the vacuum filtration can be, for example, a pressure in the range of 0.1 to 1.0 atm, preferably 0.2 to 0.6.
  • the pressure for pressure filtration can be, for example, a pressure in the range of 0.1 to 2.0 atm, preferably 0.2 to 1.0.
  • the copper powder paste according to the present invention is obtained by subjecting a filter having a pore size of 5 ⁇ m and an effective area of 9.0 cm 2 to 0.3 atm under reduced pressure to obtain a percentage of the mass permeated to the input mass of 4 g (
  • the transmittance can be 35% or more, 40% or more, 45% or more, 50% or more, 55% or more after 30 seconds, and after 1 minute, for example, 35% or more, 40% or more.
  • the filtered copper powder paste forms fine wiring and ultra-thin conductive layers (electrodes) in that the excessive copper particle size and aggregated copper powder is removed.
  • the copper powder paste before filtration is in an easily filtered state, that is, the particle size of the contained copper powder is sufficiently small and the aggregation is not sufficiently reduced, The filtering operation itself becomes difficult due to the clogging of the filter and the low recovery rate of the copper powder paste.
  • the actual operation of filtration with such a filter is easy and can achieve a sufficiently high recovery rate. It is excellent.
  • the present inventor is due to the excellent surface state of the surface-treated copper powder itself, and further the surface It is thought that it may also be caused by a combination of the treated copper powder and a carboxyl group of an organic substance (preferably a fatty acid) having a carboxyl group.
  • the copper powder used for the surface treatment a copper powder produced by a known method can be used.
  • a copper powder manufactured by a dry method or a copper powder manufactured by a wet method can be used as the copper powder.
  • the copper powder produced by the wet method is suitable in that it is a wet process consistently with the surface treatment according to the present invention.
  • the aminosilane aqueous solution is an aminosilane aqueous solution that can be used as a silane coupling agent.
  • the amount of aminosilane used is 0.025 g or more, preferably 0.050 g or more, and more preferably 0 with respect to 1 g of copper powder when the copper powder dispersion is used. 0.075 g or more, more preferably 0.10 g or more, or, for example, in amounts ranging from 0.025 to 0.500 g, 0.025 to 0.250 g, 0.025 to 0.100 g. Can be included.
  • the amount of aminosilane used is such that the volume of aminosilane at 25 ° C.
  • a silane containing one or more amino groups and / or imino groups can be used as the aminosilane.
  • the number of amino groups and imino groups contained in aminosilane can be, for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, respectively. In a preferred embodiment, the number of amino groups and imino groups contained in aminosilane can be one each.
  • An aminosilane in which the total number of amino groups and imino groups contained in the aminosilane is 1, particularly monoaminosilane, 2 aminosilanes in particular, diaminosilane, and 3 aminosilanes in particular can be called triaminosilane. .
  • Monoaminosilane and diaminosilane can be preferably used in the present invention.
  • monoaminosilane containing one amino group can be used as aminosilane.
  • the aminosilane may comprise at least one, for example one amino group, at the end of the molecule, preferably at the end of a linear or branched chain molecule.
  • aminosilanes include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 1- Aminopropyltrimethoxysilane, 2-aminopropyltrimethoxysilane, 1,2-diaminopropyltrimethoxysilane, 3-amino-1-propenyltrimethoxysilane, 3-amino-1-propynyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl- 3-
  • aminosilanes represented by the following formula I can be used.
  • R1 is a linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic, heterocyclic or non-heterocyclic, C1-C12 hydrocarbon.
  • a divalent group R2 is a C1-C5 alkyl group, R3 is a C1-C5 alkyl group or a C1-C5 alkoxy group.
  • R1 of formula I above is straight-chain or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic, heterocyclic, or heterocyclic.
  • a C1-C12 hydrocarbon divalent group more preferably R1 is a substituted or unsubstituted C1-C12 linear saturated hydrocarbon divalent group, substituted or unsubstituted, C1-C12 branched saturated hydrocarbon divalent, substituted or unsubstituted, C1-C12 straight chain unsaturated hydrocarbon divalent, substituted or unsubstituted, C1-C12 branched Unsaturated hydrocarbon divalent group, substituted or unsubstituted C1-C12 cyclic hydrocarbon divalent group, substituted or unsubstituted C1-C12 heterocyclic hydrocarbon divalent group, substituted or A group selected from the group consisting of unsubstituted C1-C12 aromatic hydrocarbon divalent groups; Rukoto can.
  • R1 in the above formula I is a C1-C12 saturated or unsaturated chain hydrocarbon divalent group, more preferably a saturated chain hydrocarbon divalent group. More preferably, the atoms at both ends of the chain structure are divalent groups having free valences.
  • the carbon number of the divalent group can be, for example, C1 to C12, preferably C1 to C8, preferably C1 to C6, preferably C1 to C3.
  • R 1 in the above formula I is — (CH 2 ) n —, — (CH 2 ) n — (CH) m — (CH 2 ) j ⁇ 1 —, — (CH 2 ) n — ( CC)-(CH 2 ) n-1 -,-(CH 2 ) n -NH- (CH 2 ) m -,-(CH 2 ) n -NH- (CH 2 ) m -NH- (CH 2 ) j -,-(CH 2 ) n-1- (CH) NH 2- (CH 2 ) m-1 -,-(CH 2 ) n-1- (CH) NH 2- (CH 2 ) m-1 -NH It can be a group selected from the group consisting of — (CH 2 ) j — (where n, m and j are integers of 1 or more).
  • R1 is — (CH 2 ) n — or — (CH 2 ) n —NH— (CH 2 ). m- .
  • the hydrogen of R1 as the above divalent group may be substituted with an amino group, for example, 1 to Three hydrogens, for example 1 to 2 hydrogens, for example 1 hydrogen, may be replaced by amino groups.
  • n, m, and j in the above formula I are each independently an integer of 1 to 12, preferably an integer of 1 to 6, more preferably an integer of 1 to 4.
  • it can be an integer selected from 1, 2, 3, 4 and can be, for example, 1, 2 or 3.
  • R2 in formula I above can be a C1-C5 alkyl group, preferably a C1-C3 alkyl group, more preferably a C1-C2 alkyl group, such as a methyl group, an ethyl group, Group, isopropyl group or propyl group, preferably methyl group or ethyl group.
  • R3 in formula I above can be a C1-C5 alkyl group, preferably a C1-C3 alkyl group, more preferably a C1-C2 alkyl group as an alkyl group, for example, It can be a methyl group, an ethyl group, an isopropyl group, or a propyl group, preferably a methyl group or an ethyl group.
  • R3 in the above formula I can be a C1-C5 alkoxy group, preferably a C1-C3 alkoxy group, more preferably a C1-C2 alkoxy group as an alkoxy group. Group, isopropoxy group or propoxy group, preferably methoxy group or ethoxy group.
  • the aminosilane aqueous solution can be mixed with copper powder by a known method.
  • stirring can be appropriately performed by a known method.
  • the mixing can be performed at room temperature, for example, at a temperature in the range of 5 to 80 ° C., 10 to 40 ° C., or 20 to 30 ° C.
  • the copper powder dispersion can be mixed and sonicated.
  • the treatment time of the ultrasonic treatment is selected according to the state of the copper powder dispersion, but is preferably 1 to 180 minutes, more preferably 3 to 150 minutes, further preferably 10 to 120 minutes, more preferably 20 to 80. Can be minutes.
  • sonication can be performed at an output of preferably 50 to 600 W, more preferably 100 to 600 W per 100 mL. In a preferred embodiment, the sonication can be performed at a frequency of preferably 10 to 1 MHz, more preferably 20 to 1 MHz, more preferably 50 to 1 MHz.
  • the copper powder in the copper powder dispersion can be recovered as a surface-treated copper powder after being subjected to a surface treatment with aminosilane and then separated from the dispersion.
  • known means can be used, for example, filtration, centrifugation, decantation, etc. can be used.
  • drying can be performed as desired.
  • a known means can be used for drying, for example, drying by heating can be performed.
  • the heat drying can be performed, for example, at a temperature of 50 to 90 ° C. or 60 to 80 ° C., for example, by a heat treatment for 30 to 120 minutes or 45 to 90 minutes.
  • the copper powder may be further pulverized as desired.
  • the recovered surface-treated copper powder is adsorbed on the surface of the copper powder that has been further surface-treated for the purpose of preventing rust or improving dispersibility in the paste. You may let them.
  • the copper powder used for the surface treatment can be a copper powder obtained by a wet method.
  • a step of preparing a slurry by adding cuprous oxide in an aqueous solvent containing an additive of gum arabic, and dilute sulfuric acid in the slurry within 5 seconds The copper powder manufactured by the method including the process of adding at once and performing a disproportionation reaction can be used.
  • the slurry can be maintained at room temperature (20 to 25 ° C.) or lower, and dilute sulfuric acid held at room temperature or lower can be added to perform the disproportionation reaction.
  • the slurry can be maintained at 7 ° C. or lower, and dilute sulfuric acid maintained at 7 ° C. or lower can be added to perform a disproportionation reaction.
  • dilute sulfuric acid can be added so that the pH is 2.5 or less, preferably pH 2.0 or less, and more preferably pH 1.5 or less.
  • the addition of dilute sulfuric acid to the slurry is within 5 minutes, preferably within 1 minute, more preferably within 30 seconds, more preferably within 10 seconds, more preferably within 5 seconds.
  • the disproportionation reaction can be completed in 10 minutes.
  • the concentration of gum arabic in the slurry can be 0.229 to 1.143 g / L.
  • cuprous oxide it is possible to use cuprous oxide used in a known method, preferably cuprous oxide particles, and the particle size of the cuprous oxide particles is a copper powder produced by a disproportionation reaction. Since it is not directly related to the particle size of the particles, coarse cuprous oxide particles can be used.
  • the principle of this disproportionation reaction is as follows: Cu 2 O + H 2 SO 4 ⁇ Cu ⁇ + CuSO 4 + H 2 O
  • the copper powder obtained by this disproportionation can be washed, rust-proof, filtered, dried, crushed, classified, and then mixed with aminosilane, if desired. Thus, after washing, rust prevention and filtration, it can be directly mixed with the aminosilane aqueous solution without drying.
  • the copper powder obtained by the disproportionation reaction has an average particle size of 0.25 ⁇ m or less as measured by a laser diffraction particle size distribution analyzer.
  • the copper powder obtained by the disproportionation reaction has a D10, D90, and Dmax measured by a laser diffraction particle size distribution measuring apparatus of [Dmax ⁇ D50 ⁇ 3, D90 ⁇ D50 ⁇ 2, D10. ⁇ D50 ⁇ 0.5], and the particle size distribution has a single peak.
  • the copper powder obtained by the disproportionation reaction has a single particle size distribution (having a single peak) as measured by a laser diffraction particle size distribution analyzer.
  • the value measured by a laser diffraction particle size distribution analyzer is [D50 ⁇ 1.5 ⁇ m], preferably [D50 ⁇ 1.0 ⁇ m], and more preferably [D50 ⁇ 0. 5 ⁇ m, Dmax ⁇ 1.0 ⁇ m].
  • a laser diffraction particle size distribution analyzer for example, SALD-2100 manufactured by Shimadzu Corporation can be used.
  • the surface-treated copper powder obtained in this way has an excellent sintering delay.
  • a sintering start temperature This is the temperature at which a certain volume change (shrinkage) occurs when the green compact made of metal powder is heated in a reducing atmosphere.
  • the temperature at which 1% volume shrinkage occurs is defined as the sintering start temperature. Specifically, it was measured as described in the examples.
  • a high sintering start temperature means that the sintering delay property is excellent.
  • the sintering start temperature of the surface-treated copper powder thus obtained is 450 ° C. or higher, preferably 500 ° C. or higher, more preferably 600 ° C. or higher, more preferably 700 ° C. or higher, More preferably 780 ° C. or higher, more preferably 800 ° C. or higher, more preferably 810 ° C. or higher, more preferably 840 ° C. or higher, more preferably 900 ° C. or higher, more preferably 920 ° C. or higher, more preferably 950 ° C. or higher. be able to.
  • the sintering start temperature of Ni ultrafine powder (average particle size 0.2 to 0.4 ⁇ m), which has been conventionally used when a high sintering start temperature is required, is in the range of 500 to 600 ° C.
  • the surface-treated copper powder uses Cu, which is cheaper and easier to obtain than Ni, and is a fine particle, but has an excellent or better sintering delay.
  • the surface-treated copper powder can form a sintered body by heating the green compact in a reducing atmosphere.
  • the obtained sintered body is formed as an excellent electrode.
  • This sintering process can be suitably used particularly for the production of the internal electrode of a chip multilayer ceramic capacitor.
  • This sintered body can be suitably used particularly as an internal electrode of a chip multilayer ceramic capacitor.
  • the SiO 2 particles are dispersed in the cross section of the electrode, enabling the formation of an ultrathin electrode and at the same time not reducing the reliability (quality) of the electrode.
  • the surface-treated copper powder has a Si adhesion amount of generally 500 to 16000 ⁇ g, preferably 500 to 3000 ⁇ g, per 1 g of copper powder.
  • This Si adhesion amount can be determined by ICP (inductively coupled plasma atomic emission spectrometry).
  • it may further contain 0.05 wt% or more of N with respect to the weight of the copper powder.
  • the mechanism by which the silane coupling agent is adsorbed on the copper powder is unknown, but the present inventor believes that it is adsorbed by an interaction between the nitrogen of the amino group at the end of the silane coupling agent and copper. .
  • the surface-treated copper powder has a Si-containing layer thickness (Si thickness) formed by the surface treatment of generally 0.6 to 25 nm, preferably 1.0 to 25 nm, more preferably Can be from 1.5 to 20 nm.
  • the thickness of the Si-containing layer (Si thickness) means that the abundance ratio of Si atoms with respect to all atoms is maximum in a cross section of the surface of the surface-treated copper powder as measured by EDS (energy dispersive X-ray analysis)
  • EDS energy dispersive X-ray analysis
  • the cross section of the surface of the surface-treated copper powder is selected from among at least 100 or more copper powder particles observed in the sample section, and the clearest boundary of each is selected and the surface-treated copper powder is cross-sectioned. Measurement and tabulation can be performed by treating the cross section as being perpendicular to the surface.
  • the surface-treated copper powder has a weight percentage of N with respect to the copper powder of, for example, 0.05% by weight or more, preferably 0.06% by weight or more, and more preferably 0.07% by weight or more.
  • N with respect to the copper powder
  • it can be 0.05 to 0.50% by weight, preferably 0.06 to 0.45% by weight, and more preferably 0.08 to 0.40% by weight.
  • the weight% of N with respect to the copper powder can be calculated from the generated NO 2 by melting the copper powder at a high temperature.
  • the surface-treated copper powder has a surface N of, for example, 1.0% or more, preferably 1.4% or more, more preferably, in a survey measurement by XPS (X-ray photoelectron spectroscopy) analysis. Is 1.5% or more, more preferably 1.6% or more, or, for example, 1.0 to 6.0%, preferably 1.4 to 6.0%, more preferably 1.5 to 6.0%. More preferably, it is in the range of 1.6 to 6.0%, and the N photoelectrons are, for example, 1000 cps (count per second) or more, preferably 1200 cps or more, or, for example, 1000 to 9000 cps, preferably 1200 to 8000 cps. It can be assumed that
  • the surface-treated copper powder has surface Si of, for example, 0.6% or more, preferably 0.8% or more, more preferably, as measured by a survey measurement by XPS (X-ray photoelectron spectroscopy) analysis.
  • Si Si of, for example, 0.6% or more, preferably 0.8% or more, more preferably, as measured by a survey measurement by XPS (X-ray photoelectron spectroscopy) analysis.
  • Si photoelectrons are, for example, 1000 cps (count per second) or more, preferably 1200 cps or more, is there For example 1000 ⁇ 12
  • the surface-treated copper powder may be further subjected to a surface treatment after being subjected to a surface treatment with aminosilane.
  • a surface treatment for example, a rust prevention treatment with an organic rust inhibitor such as benzotriazole or imidazole can be given, and even with such a normal treatment, the surface treatment with aminosilane is not eliminated. . Therefore, a person skilled in the art can perform such a known surface treatment as desired within a limit not losing the excellent sintering retardance. That is, the copper powder and the copper powder paste obtained by further surface-treating the surface of the surface-treated copper powder according to the present invention within the limit not losing the excellent sintering delay property are also the present invention. Within range.
  • the present invention even when a metal powder other than the copper powder is used, excellent characteristics can be obtained by the surface treatment described above for the copper powder. Even when a metal powder other than copper powder is used, the present invention can be carried out according to the preferred embodiment described for the copper powder.
  • the metal powder for example, any metal powder of Pt, Pd, Ag, Ni, Cu can be used. Examples of preferable metal powder including copper powder include Ag, Ni, and Cu.
  • the present invention can be suitably implemented as described above by the adhesion of Si, but can also be suitably implemented by the deposition of elements other than Si. Even when an element other than Si adheres, the present invention can be implemented by the preferred embodiment described for Si. As elements other than Si, any one or more of Ti, Al, Zr, Ce, and Sn can be cited. Preferable elements including Si include one or more of Si, Ti, Al, Zr, Ce, and Sn, and more preferably any one or more of Si, Ti, and Al.
  • the present invention can be suitably implemented by performing a surface treatment with a silane coupling agent, but also by performing a surface treatment with a coupling agent other than the silane coupling agent, It can implement suitably.
  • Examples of coupling agents other than silane coupling agents include titanate and aluminate.
  • Si when a silane coupling agent is used as the coupling agent, Si, when titanate is used, Ti, and when aluminate is used, Al can be suitably attached.
  • the mode of use of these coupling agents can be as described above for silane coupling agents. Similar to the structure of the silane coupling agent, in the structure of titanate and aluminate, a structure in which a substituent containing an amino group at the terminal is coordinated to Ti and Al as the central atoms is preferable.
  • the suitable adhesion amount of Si, Ti or Al by such a coupling agent is as described above for the copper powder, and for example, 200 g per 1 g of the metal powder.
  • the thickness (Si thickness) of the Si-containing layer formed by the surface treatment of the metal powder can be as described above for the copper powder, and the thickness of the Ti-containing layer (Ti thickness).
  • the thickness of the Al-containing layer (Al thickness) can also be set as described above for the thickness of the Si-containing layer (Si thickness).
  • the surface-treated metal powder can have the surface Si as described above for the copper powder in the survey measurement of XPS (X-ray photoelectron spectroscopy) analysis.
  • Ti and Al can be set to a numerical range similar to the numerical range defined for Si by the same measurement method as Si.
  • the surface-treated metal powder can have the surface N as described above for the copper powder in the survey measurement of the XPS (X-ray photoelectron spectroscopy) analysis method.
  • the process for producing the metal powder paste can be performed according to the procedure as described above for the copper powder paste.
  • organic substances such as fatty acids, solvents, binder resin types, and mixing ratios that can be suitably used are as described above for the copper powder paste.
  • the metal powder paste thus obtained has the same excellent characteristics as described above for the copper powder paste in a preferred embodiment, and also has excellent filter permeability, handling properties, and firing. Has delaying properties and the like.
  • R1 of the above formula II the groups exemplified as R1 of the above formula I can be preferably used.
  • R2 of the above formula II the groups exemplified as R2 of the above formula I can be preferably used.
  • a C3 alkyl group can be exemplified, and particularly preferably, a propyl group and an isopropyl group can be exemplified.
  • plain act KR44 manufactured by Ajinomoto Fine Techno Co.
  • the metal powder according to the present invention has a high sintering start temperature, and by blending this, an excellent conductive metal powder paste can be produced, An excellent electrode can be manufactured by sintering this conductive metal powder paste.
  • the sintering start temperature with the metal powder of the present invention is as described above for the copper powder.
  • the electrode obtained according to the invention can be as described above for SiO 2 in the electrode cross section, likewise TiO 2 in the electrode cross section and / or Al 2 O 3 in the electrode cross section.
  • the SiO 2 in the electrode cross section the size, number and density as described above can be used.
  • the SiO 2 of the electrode cross section corresponds to the case where a silane coupling agent is used as the coupling agent for the surface treatment, and the titanate as the coupling agent for the surface treatment for the TiO 2 of the electrode cross section.
  • Al 2 O 3 in the electrode cross section corresponds to the case where aluminate is used as a surface treatment coupling agent.
  • the present invention will be described in more detail with reference to examples.
  • the present invention is not limited to the following examples.
  • the surface-treated copper powder was manufactured as follows. [Milling by wet method] 20 g of copper powder subjected to the surface treatment was produced by a wet method. The obtained copper powder had the following characteristics. For the measurement, a laser diffraction particle size distribution measuring device (SALD-2100 manufactured by Shimadzu Corporation) was used. D50 0.12 ⁇ m Distribution
  • silane Diaminosilane A-1120 (made by MOMENTIVE) Aminosilane A-1110 (made by MOMENTIVE) Epoxy silane Z-6040 (manufactured by Toray Dow Corning) Methyltrimethoxysilane KBM-13 (manufactured by Shin-Etsu Silicone) 3-Phenylaminopropyltrimethoxysilane (made by MOMENTIVE) The concentration was adjusted in the range of 0.5 to 15 vol%. Moreover, pH was adjusted to 4 with dilute sulfuric acid except amino silane.
  • the temperature was continuously increased to a rate of 5 ° C./minute and a measurement range: 50 to 1000 ° C., and the height change (expansion / shrinkage change) of the compact was automatically recorded.
  • the temperature at which the height change (shrinkage) of the molded body started and the shrinkage rate reached 1% was defined as “sintering start temperature”.
  • the measurement results of the sintering start temperature of the surface-treated copper powder for each example and comparative example are summarized in Table 3.
  • Adhesion amount Si The surface-treated copper powder is dissolved with an acid, quantified by ICP (inductively coupled plasma atomic emission spectrometry), and adhered to the unit mass (g) of the surface-treated copper powder. The mass ( ⁇ g) of was determined. N, and C ⁇ ⁇ ⁇ copper powder is melted at a high temperature, generated NO 2, deposited from CO 2 N, to calculate the amount of C, to measure the N, the amount of C which stuck to the entire surface of the copper powder The mass% (% by weight) of the mass of N and C adhering to the mass of the surface-treated copper powder was determined.
  • tetraethoxysilane (TEOS) was used as a silane coupling agent, and copper powder was surface-treated using ammonia as a catalyst.
  • TEOS tetraethoxysilane
  • the surface-treated copper powder obtained was agglomerated, and it was considered that a uniform surface treatment and particle size were not obtained by visual observation.
  • the particle size distribution was one peak before the surface treatment, and two peaks.
  • the surface-treated copper powder produced by mixing the aminosilane aqueous solution according to the present invention is a copper powder having a very small size even though the production method is extremely simple.
  • the sintering start temperature was higher than or equal to that of fine powder of high melting point metal such as nickel.
  • a sintered body can be manufactured by sintering similar to the manufacturing process of the electrode of the chip multilayer ceramic capacitor, and the cross section of the sintered body thus manufactured (formed) It was found that SiO 2 particles were dispersed in the.
  • the silane coupling agent needs to be an aminosilane having an amino group.
  • an aminosilane it turned out that the aminosilane which has an amino group at the terminal is preferable.
  • Comparative Example 4 although it seems that a sufficient amount of Si is attached to the copper powder, a sufficient sintering delay is not realized. The reason for this is unclear, but in the Comparative Example 4, the present inventor does not have an aminosilane having a structure having an amino group at the terminal, and in addition, the benzene ring is present at the terminal rather than the amino group. Furthermore, it is not because a state like steric hindrance has occurred, and aminosilane or Si once attached to the copper powder is detached from the copper powder at an early stage during the temperature rise for sintering. I guess.
  • an aminosilane aqueous solution 50 mL was added and stirred for 60 minutes.
  • rotating blades 300 rpm + ultrasound (manufactured by Techjam Co., Ltd., ultrasonic cleaner 3 frequency type / W-113) (output) 100 W, frequency 100 kHz) was performed.
  • processing of only rotating blades (300 rpm) and processing of only ultrasonic waves were performed separately.
  • Diaminosilane A-1120 manufactured by MOMENTIVE
  • aminosilane A-1110 manufactured by MOMENTIVE
  • the surface-treated fine copper powder was obtained by integrated production.
  • the surface-treated copper powder obtained in this way has excellent sintering retardancy and, at the same time, SiO 2 present in the cross section of the sintered body, like the surface-treated copper powder of the above-mentioned Examples.
  • the number of large particles was small.
  • this integrated production can be performed without drying until a final product is obtained, which is simple and excellent in workability.
  • the copper powder surface-treated with diaminosilane exhibits a remarkably excellent transmittance of at least 9 to 10 times or more under any conditions as compared with the comparative example.
  • the electrode When the filtered and filtered copper powder paste was applied to a thickness of about 1 ⁇ m on a dielectric powder paste sheet, a uniform sheet of copper powder paste could be easily obtained. When this was sintered, the electrode could be manufactured without peeling off the dielectric layer and the conductive layer made of copper.
  • the copper powder paste according to the present invention is excellent in sintering delay, in addition, aggregation is prevented and filter permeability is excellent. Therefore, it was found that it can be suitably used for electrode production using a printing technique.
  • Example 12 The copper powder subjected to the rust prevention treatment (Example 12) was evaluated in the same manner as in Example 4 described above, and the results are summarized in Tables 6 to 8.
  • the size of the copper powder after the treatment in Table 7 is the size of the copper powder after the rust prevention treatment in Example 12, and each evaluation in Table 8 is also the result of the copper powder subjected to the rust prevention treatment. . From these results, it was found that the excellent properties of the surface-treated copper powder were not lost even when the surface-treated copper powder was rust-proofed.
  • Examples 18 to 20 and Comparative Example 11 20 g of copper powder subjected to the surface treatment was produced by the wet method described above. That is, (1) 50 g of cuprous oxide was added to 0.4 g of gum arabic + 350 mL of pure water. (2) Next, 50 mL of dilute sulfuric acid (25 wt%) was added at a time. (3) This was stirred with a rotary blade (300 rpm ⁇ 10 minutes) and left for 60 minutes. (4) Next, the precipitate was washed. In the washing, first, the supernatant was removed, 350 mL of pure water was added and stirred (300 rpm ⁇ 10 minutes), and then left for 60 minutes.
  • Example 13 According to Japanese Patent No. 4164209, copper powder was obtained by a chemical reduction method. That is, 2 g of gum arabic was added to 2900 mL of pure water, and then 125 mL of copper sulfate was added and 360 mL of 80% hydrazine monohydrate was added while stirring. After the addition of hydrazine monohydrate, the temperature was raised from room temperature to 60 ° C. over 3 hours, and copper oxide was further reacted over 3 hours. After completion of the reaction, the resulting slurry was filtered with Nutsche, then washed with pure water and methanol, and further dried to obtain copper powder. This copper powder and a diaminosilane coupling agent aqueous solution were mixed in the procedure of Example 1 to obtain a surface-treated silver powder. This characteristic was evaluated by the procedure of Example 1.
  • Nickel powder As the nickel powder, NF32 (D50 0.3 ⁇ m) manufactured by Toho Titanium was used.
  • the silver powder thus obtained was filtered with Nutsche, washed with pure water and alcohol in that order, and dried at 70 ° C. for 12 hours in an air atmosphere. This silver powder was dry-classified to finally obtain a silver powder having a D50 of 0.1 ⁇ m and a Dmax of 0.5 ⁇ m.
  • silane Diaminosilane A-1120 (made by MOMENTIVE) Methyltrimethoxysilane KBM-13 (manufactured by Shin-Etsu Silicone) Titanate: Amino group-containing plain act KR44 (manufactured by Ajinomoto Fine Techno Co., Ltd.) Amino group-free plain act KR TTS (Ajinomoto Fine Techno Co., Ltd.) The concentration was adjusted in the range of 1 to 10 vol%. Further, the pH was adjusted to 4 with dilute sulfuric acid except for the amino coupling agent.
  • Diaminosilane A-1120 H 2 N—C 2 H 4 —NH—C 3 H 6 —Si (OCH 3 ) 3 Methyltrimethoxysilane
  • KBM-13 H 3 C—Si (OCH 3 ) 3
  • Amino group-containing plain act KR44 Side chain organic functional group of hydrophobic group (CH 3 ) 2 CH—O— Side chain organic functional group of hydrophilic group —O— (C 2 H 4 ) —NH— (C 2 H 4 ) —NH 2 Amino group-free plain act KR TTS Side chain organic functional group of hydrophobic group (CH 3 ) 2 CH—O— Side chain organic functional group of hydrophilic group —O—CO— (C 17 H 35 )
  • Example 14 Diaminosilane treatment with silane concentration of 1 vol% Surface-treated silver powder of Example 16: Diaminosilane treatment with silane concentration of 1 vol% Surface treated copper powder of Example 19: Amino group-containing titanate treatment with titanate concentration 6 vol% Surface-treated nickel powder of Example 22: Amino group-containing titanate treatment with a titanate concentration of 6 vol% Surface-treated silver powder of Example 25: Amino group-containing titanate treatment with a titanate concentration of 6 vol% Silver powder of Comparative Example 7: No surface treatment Surface-treated silver powder of Comparative Example 8: Methyltrimethoxysilane treatment with silane concentration of 10 vol% Nickel powder of Comparative Example 9: No surface treatment Surface-treated nickel powder of Comparative Example 10: Methyltrimethoxysilane treatment with silane concentration of 10 vol% Surface-treated copper powder of Comparative Example 11: Titanate treatment having no amino group with a silane concentration of 10 vol% Fatty acid: Oleic acid (C18, 1 double bond
  • the surface-treated metal powder was produced using a metal powder other than copper powder or using a coupling agent other than aminosilane
  • the copper powder surface-treated with aminosilane As in the case, it was found that a high sintering start temperature can be obtained by a very simple manufacturing method.
  • a sintered compact can be manufactured from these surface-treated metal powders by the same sintering as the manufacturing process of the electrode of the chip multilayer ceramic capacitor.
  • the metal powder paste produced from these surface-treated metal powders, as well as the copper powder paste has excellent sintering retardancy, and prevents aggregation and filter permeation. It has also been found that it is excellent in performance and can be suitably used for electrode production using a printing technique.
  • the copper powder paste according to the present invention has excellent sintering delay and dispersibility of the copper powder in the paste, so that it avoids manufacturing problems such as electrode peeling and chip stacking.
  • the production of the capacitor electrode can be advantageously performed.
  • the copper powder paste according to the present invention can be manufactured by performing a very simple process on the surface-treated copper powder, it does not require advanced skills and is excellent in workability and productivity. Is.
  • the metal powder paste according to the present invention has excellent characteristics as well as the copper powder paste.
  • the present invention is an industrially useful invention.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Physics & Mathematics (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Conductive Materials (AREA)
  • Powder Metallurgy (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
  • Ceramic Capacitors (AREA)
  • Manufacturing Of Electric Cables (AREA)

Abstract

L'invention concerne une pâte de poudre de métal traitée en surface dont l'usage convient pour produire une électrode pour un condensateur en puce céramique multicouche et qui a d'excellentes propriétés de retard de frittage, et son procédé de production. La présente invention est constituée d'une pâte de poudre de métal qui comprend : une poudre de métal traitée en surface dans laquelle la quantité d'adhésion d'au moins l'un des éléments Si, Ti, Al, Zr, Ce et Sn est comprise entre 200 et 16000 µg par rapport à 1 g de poudre de métal et N est supérieur ou égal à 0,02 % en pourcentage en poids par rapport à la poudre de métal ; et une substance organique ayant un groupe carboxyle, la poudre de métal traitée en surface et la substance organique étant dispersées dans un solvant.
PCT/JP2013/054415 2012-02-21 2013-02-21 Pâte de poudre de métal et son procédé de production WO2013125659A1 (fr)

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JP2014500934A JP6212480B2 (ja) 2012-02-21 2013-02-21 金属粉ペースト、及びその製造方法
CN201380010167.XA CN104115237B (zh) 2012-02-21 2013-02-21 金属粉糊及其制造方法

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CN105321711A (zh) * 2014-07-31 2016-02-10 住友金属矿山株式会社 导电浆料
JP2016033850A (ja) * 2014-07-30 2016-03-10 Jx日鉱日石金属株式会社 導電性ペースト及びその製造方法
KR20200014695A (ko) 2018-08-01 2020-02-11 제이엑스금속주식회사 세라믹스층과 구리 분말 페이스트 소결체의 적층체
KR20200014696A (ko) 2018-08-01 2020-02-11 제이엑스금속주식회사 세라믹스층과 구리 분말 페이스트 소결체의 적층체
WO2020059291A1 (fr) 2018-09-21 2020-03-26 Ｊｘ金属株式会社 Poudre de cuivre facilement broyable et son procédé de fabrication

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JP5843821B2 (ja) * 2013-08-13 2016-01-13 Jx日鉱日石金属株式会社 金属粉ペースト、及びその製造方法
CN105086419B (zh) * 2015-08-11 2017-08-01 东华大学 一种可电镀性含氟聚酰亚胺改性工程塑料合金及其制备方法
JP6630208B2 (ja) * 2016-03-28 2020-01-15 Ｊｘｔｇエネルギー株式会社 金属粉ペーストの製造方法、金属粉ペーストのスクリーン印刷方法、電極の製造方法、チップ積層セラミックコンデンサーの製造方法および金属粉ペースト
MY194769A (en) * 2016-04-28 2022-12-15 Hitachi Chemical Co Ltd Copper paste for joining, method for manufacturing joined body, and method for manufacturing semiconductor device
KR102217288B1 (ko) * 2018-08-16 2021-02-19 삼성전기주식회사 적층 세라믹 전자부품 및 그 제조방법

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Publication number Priority date Publication date Assignee Title
JP2016033850A (ja) * 2014-07-30 2016-03-10 Jx日鉱日石金属株式会社 導電性ペースト及びその製造方法
CN105321711A (zh) * 2014-07-31 2016-02-10 住友金属矿山株式会社 导电浆料
CN105321711B (zh) * 2014-07-31 2018-11-16 住友金属矿山株式会社 导电浆料
KR20200014695A (ko) 2018-08-01 2020-02-11 제이엑스금속주식회사 세라믹스층과 구리 분말 페이스트 소결체의 적층체
KR20200014696A (ko) 2018-08-01 2020-02-11 제이엑스금속주식회사 세라믹스층과 구리 분말 페이스트 소결체의 적층체
US11056279B2 (en) 2018-08-01 2021-07-06 Jx Nippon Mining & Metals Corporation Laminate of ceramic layer and sintered body of copper powder paste
US11069478B2 (en) 2018-08-01 2021-07-20 Jx Nippon Mining & Metals Corporation Laminate of ceramic layer and sintered body of copper powder paste
WO2020059291A1 (fr) 2018-09-21 2020-03-26 Ｊｘ金属株式会社 Poudre de cuivre facilement broyable et son procédé de fabrication
KR20210058910A (ko) 2018-09-21 2021-05-24 제이엑스금속주식회사 용이 해쇄성 구리 분말 및 그 제조 방법
US11920215B2 (en) 2018-09-21 2024-03-05 Jx Metals Corporation Easily-crushable copper powder and manufacturing method therefor

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TWI527069B (zh) 2016-03-21
TW201344723A (zh) 2013-11-01
KR101769337B1 (ko) 2017-08-18
CN104115237B (zh) 2018-09-07

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